Ozone treatment of surface of membrane to improve permselectivity

ABSTRACT

A surface modified gas separation membrane having improved permselective properties for separating a mixture of gases as compared to the unmodified membrane, is described. The gas separation membrane is made by a process comprising the steps of coating a surface unmodified gas separation membrane with a solution of a coating material, wherein the coating material is an organic material having at least one site of unsaturation; heating the coated gas separation membrane; and contacting the heated coated gas separation membrane with at least one oxidizing agent for a time effective to surface modify the gas separation membrane to produce the surface modified gas separation membrane having improved permselectivity.

This application is a divisional application of Ser. No. 09/226,524,filed, Dec. 30, 1998, now U.S. Pat. No. 6,156,381.

TECHNICAL FIELD

The invention relates generally to gas separation membranes. Inparticular, the present invention relates to a surface modified gasseparation membrane, wherein the membrane has improved permselectiveproperties to separate a mixture of gases as compared to the unmodifiedmembrane.

BACKGROUND OF THE INVENTION

Fluid permeable membranes fabricated from a wide variety of polymershave been used extensively to separate gases, such as oxygen, nitrogen,carbon dioxide, methane, hydrogen, and other gases from gas mixtures.The efficiency of the fluid separation process is determined by theproperties of fluid mixture, the membrane material and its structure.Preferably, the gas separation membrane is highly selective, i.e. themembrane has a high separation factor, high gas permeability, and isresistant to chemicals and temperature variations, and is mechanicallystrong. However, membranes with high selectivity are generallycharacterized by low permeability, while membranes with highpermeability generally possess unacceptably low separation factors.

A variety of methods for enhancing the selectivity of fluid permeablemembranes by modifying the characteristics of the membrane have beendescribed. For example, Kramer et al, U.S. Pat. No. 5,215,554 describe amethod for enhancing selectivity by modifying the interstices orrecesses of the membrane substantially throughout the thickness of thegas permeable membrane. U.S. Pat. Nos. 4,311,573, 4,589,964 and4,968,532, disclose graft polymerization of a monomer on to a preformed,saturated polymer substrate which has been subjected to ozonizationprior to grafting. See also U.S. Pat. Nos. 4,486,202; 4,575,385;4,654,055 and 4,728,346. Halogenation treatment techniques have alsobeen used to modify gas separation membranes. See U.S. Pat. Nos.3,062,905 and 4,828,585.

Although several methods that improve selectivity of specific membraneshave been described, including surface modification methods, suchmethods have several disadvantages—long exposure times, high chemicalconcentrations and high treatment temperatures, and possibly,degradation of the membrane. Thus there is a need for an improved andcost-effective gas separation membrane which possesses high gaspermeability and a high separation factor. The current method provides acost-effective gas separation membrane with a significant improvement inselectivity with a commercially acceptable loss of permeability.

SUMMARY OF THE INVENTION

The present invention relates to a method for preparing a surfacemodified gas separation membrane, wherein the membrane has improvedpermselective properties for separating a mixture of gases as comparedto the unmodified membrane. The method comprises coating a surfaceunmodified gas separation membrane with a solution of a coatingmaterial, wherein the coating material is an organic material having atleast one site of unsaturation; heating the coated gas separationmembrane; and contacting the heated coated gas separation membrane withat least one oxidizing agent for a time effective to surface modify thegas separation membrane to produce the surface modified gas separationmembrane having improved permselectivity.

In one aspect, the invention relates to a method for preparing a surfacemodified gas separation membrane, wherein said membrane has improvedpermselective properties for separating a mixture of gases as comparedto the unmodified membrane, comprising:

(a) providing a surface unmodified gas separation membrane;

(b) providing a solution of a coating material, wherein said coatingmaterial is an organic material having at least one site ofunsaturation;

(c) contacting the surface unmodified gas separation membrane with thesolution of the coating material;

(d) coating said coating material on the surface unmodified gasseparation membrane to produce a coated gas separation membrane;

(e) optionally removing substantially all of the residual coatingmaterial from the surface of the coated gas separation membrane of step(d);

(f) optionally removing substantially all of the solvent from thesurface of the coated gas separation membrane of step (d) or (e) bycontacting the surface with at least one anhydrous non-oxidizing gas;

(g) heating the coated gas separation membrane of step (d), (e), or (f)at about 10° C. to about 150° C.;

(h) contacting the heated coated gas separation membrane of step (g)with at least one oxidizing agent for a time effective to surface modifythe gas separation membrane between about 5 minutes and 24 hours toproduce the surface modified gas separation membrane having improvedpermselectivity; and

(i) optionally contacting the surface oxidized gas separation membraneof step (h) with a non-oxidizing gas for a time effective to removesubstantially all of the oxidizing gas to produce the surface modifiedgas separation membrane having improved permselectivity.

In an alternative embodiment, the method for preparing a surfacemodified gas separation membrane further comprises:

(j) contacting the treated gas separation membrane of step (h) or (i)with at least one oxidizing agent for a time effective to surface modifythe gas separation membrane between about 5 minutes and 24 hours toproduce the surface modified gas separation membrane having improvedpermselectivity; and

(K) optionally contacting the surface oxidized gas separation membraneof step (j) with a non-oxidizing gas for a time effective to removesubstantially all of the oxidizing gas to produce the surface modifiedgas separation membrane having improved permselectivity.

In a preferred embodiment, the gas separation membrane is amelt-extruded symmetric flat sheet, a solvent cast symmetric flat sheet,an asymmetric flat sheet, or an asymmetric hollow fiber. In a morepreferred embodiment, the gas separation membrane is an asymmetrichollow fiber.

In a preferred embodiment, the coating material is an organic materialhaving at least one site of unsaturation. In a preferred embodiment thecoating material is a low molecular weight polymeric material or asurfactant. In a more preferred embodiment, the low molecular weightpolymeric material has a molecular weight that ranges from about 1000 toabout 100,000.

In a preferred embodiment, permselectivity of the surface modified gasseparation membrane is increased by about 5% to about 30% as compared tothe surface unmodified membrane.

In an alternative embodiment, the invention relates to a method forpreparing a surface modified gas separation membrane, wherein saidmembrane has improved permselective properties for separating a mixtureof gases as compared to the unmodified membrane, comprising:

(a) providing a surface unmodified gas separation membrane;

(b) providing a solution of a coating material, wherein said coatingmaterial is an organic material having at least one site ofunsaturation;

(c) heating the solution of the coating material at about 10°C. to about150° C.;

(d) optionally heating the surface unmodified gas separation membrane atabout 10° C. to about 150° C.;

(e) contacting the surface unmodified gas separation membrane with theheated solution of the coating material;

(f) coating said heated coating material on the surface unmodified gasseparation membrane to produce a coated gas separation membrane;

(g) optionally removing substantially all of the residual coatingmaterial from the surface of the coated gas separation membrane of step(f);

(h) optionally removing substantially all of the solvent from thesurface of the coated gas separation membrane of step (f) or (g) bycontacting the surface with at least one anhydrous non-oxidizing gas;

(i) contacting the heated coated gas separation membrane of step (h)with at least one oxidizing agent for a time effective to surface modifythe gas separation membrane between about 5 minutes and 24 hours toproduce the surface modified gas separation membrane having improvedpermselectivity; and

(j) optionally contacting the surface oxidized gas separation membraneof step (i) with a non-oxidizing gas for a time effective to removesubstantially all of the oxidizing gas to produce the surface modifiedgas separation membrane having improved permselectivity.

In an alternative embodiment, the method for preparing a surfacemodified gas separation membrane further comprises:

(k) contacting the treated gas separation membrane of step (i) or (j)with at least one oxidizing agent for a time effective to surface modifythe gas separation membrane between about 5 minutes and 24 hours toproduce the surface modified gas separation membrane having improvedpermselectivity; and

(l) optionally contacting the surface oxidized gas separation membraneof step (k) with a non-oxidizing gas for a time effective to removesubstantially all of the oxidizing gas to produce the surface modifiedgas separation membrane having improved permselectivity.

It is a particularly surprising element of the invention that thepermselectivity of the gas separation membrane for gas mixtures can beincreased substantially and, in a cost-effective manner, as compared tothe selectivity observed for the unmodified polymers and other modifiedmembranes known in the art. Additionally, the membranes can beadvantageously incorporated in portable units.

These and other embodiments of the present invention will readily occurto those of ordinary skill in the art in view of the disclosure herein.

DETAILED DESCRIPTION

Before describing the present invention in detail, it is to beunderstood that this invention is not limited to particular formulationsor process parameters as such may, of course, vary. It is also to beunderstood that the terminology and examples used herein are for thepurpose of describing particular embodiments of the invention only, andare not intended to be limiting.

The practice of the present invention will employ, unless otherwiseindicated, conventional techniques of chemistry and engineering whichare within the skill of the art. Such techniques are explained fully inthe literature. See, e.g., Kesting, R. E., Synthetic PolymericMembranes, John Wiley & Sons, 2 ^(nd) Ed. (1985); Hwang, Sun-Tak andKammermeyer, Karl, Membranes in Separation, Robert E. Kriegar PublishingCo., Inc., (1984). Although a number of compositions and methods similaror equivalent to those described herein can be used in the practice ofthe present invention, the preferred materials and methods aredescribed.

All patents, patent applications, and publications mentioned herein,whether supra or infra, are hereby incorporated by reference in theirentirety.

It must be noted that, as used in this specification and the appendedclaims, the singular forms “a”, “an”, and “the” include plural referentsunless the content clearly dictates otherwise. Thus, for example,reference to “a gas separation membrane” includes two or more suchmembranes and the like.

The present invention provides a method for preparing a surface modifiedgas separation membrane, wherein the membrane has improved permselectiveproperties. The method is used to separate oxygen, nitrogen, carbondioxide, methane, hydrogen, and other gases from gas mixtures.

To improve selectivity with a commercially acceptable reduction in gaspermeability, the surface unmodified gas separation membrane mustdemonstrate adequate mechanical strength and moderate to high gaspermeability rates. Preferably, the gas separation membrane possessesadequate gas selectivity, gas permeability, chemical resistance,temperature resistance, and mechanical strength. Gas permeability isdefined as the ratios of [(amount of permeate) (membrane thickness)]divided by [(area) (time) (driving force gradient across the membrane)].A standard permeability measurement unit is a Barrer (Ba), wherein 1Ba=1×10⁻¹⁰ cc-cm/cm²-sec-cm of Hg. A standard measure of flux is a gaspermeation unit (GPU), wherein 1GPU=1×10⁻⁶ cc/cm²-sec-cm of Hg.Permselectivity, selectivity or alpha, i.e. the separation factor, isthe ratio of the permeability of the faster permeating gas to thepermeability of the slower permeating gas. Polymers suitable for suchgas separation membranes have been described in the art. See, forexample, The Polymer Handbook, J. Brandrup and E. H. Immergut, editors,2nd edition, John Wiley & Sons, New York, 1975. Semi-permeable polymericmaterial suitable for such gas separation membranes include, preferablyolefinic polymers, such as poly-4-methylpentene, polyethylene,polyphenylene oxides and polypropylene; polytetrafluoroethylene;cellulosic esters, ethyl cellulose, cellulose ethers, and regeneratedcellulose; polyetherketones and polyetheretherketones;polyestercarbonates; polycarbonates, including ring substituted versionsof bisphenol based polycarbonates; polyimides, polyetherimides,polyamides, polyamideimides; polyethersulfones, polysulfones,polyarylates, polyesters, styrenic polymers including polystyrenes,styrene-acrylonitrile copolymers (for example, TYRIL™,styrene-acrylonitrile resin, trademark of Dow Chemical Company),poly(4-vinylanisole4-vinylpyridine), acrylonitrile-butadience-styrene(ABS) terpolymers and the like, including blends and copolymers thereof.More preferred membrane materials include polyethersulfones andpolyarylates.

Gas separation membranes of the invention may be homogeneous, symmetric,asymmetric, or composite membranes, as described in U.S. Pat. No.4,874,401. Preferably the gas separation membranes of the invention areasymmetric or composite. The gas separation membranes may be formed by anumber of methods known in the art, such as solution casting,compression molding, and extrusion. See, for example, U.S. Pat. No.4,961,760. In addition, the gas separation membranes may be shaped inthe form of flat films or sheets, hollow fibers, hollow tubes or spiralwound membranes and the like. Thus the gas separation membrane may be amelt-extruded symmetric flat sheet, a solvent cast symmetric flat sheet,an asymmetric flat sheet, or an asymmetric hollow fiber. In a preferredembodiment, the gas separation membrane is an asymmetric hollow fiber.

The surface unmodified gas separation membrane is contacted with asolution of a coating material. The coating material is an organicmaterial having at least one site of unsaturation; and is preferably asurfactant or a low molecular weight polymeric material, wherein themolecular weight of the polymeric material ranges from about 1000 toabout 100,000. Organic materials suitable for such coating materialsinclude surfactants; monomers and polymers of aromatic compounds, suchas phenol, sodium- or potassium-phenate, anisole, butylether,polycarbonates, including ring substituted versions of bisphenol basedpolycarbonates; polyimides, polyetherimides, polyamides,polyamideimides; polyethersulfones, polysulfones, polystyrenes,polyarylates, polyesters; and the like, including blends and copolymersthereof. In a preferred embodiment, the coating material comprisespolymeric material having pendant phenyl groups, more preferably thependant groups are terminal phenyl groups. In an alternative embodiment,the coating material comprises polymeric material wherein the interiorphenyl rings have substitutents including 1-4C containing alkyl groups,halides, and the like, and further wherein the polymeric materialcomprises an unsubstituted terminal phenyl ring. In another preferredembodiment, the coating material is a surfactant, including but notlimited to, Triton X-100, Triton X-114, and the like. In one embodiment,substantially all of the residual coating material is removed from thesurface of the coated gas separation membrane prior to further treatmentof the membrane. In another embodiment, substantially all of the solventfrom the surface of the coated gas separation membrane is removed, bycontacting the surface with at least one anhydrous non-oxidizing gas,prior to further treatment of the membrane. The non-oxidizing gas isselected from nitrogen, air, helium, carbon dioxide and combinationsthereof. In a preferred embodiment, the non-oxidizing gas is nitrogen.

The coated gas separation membrane is heated at an appropriatetemperature for a suitable period of time, wherein the time ranges frombetween about 5 minutes to about 24 hours. A wide range of temperaturesmay be used, preferably in a range between temperatures sufficientlybelow the softening or melting point of the polymeric material used forthe membrane, and above the temperature where stress cracking of thepolymers substantially occurs. Thus a temperature which does notadversely affect the surface unmodified membrane, i.e. melting orcracking, and where the surface ozonization reaction occurs at areasonable rate may be used. Further, temperature can be used to controlthe reaction rate. In one embodiment, the coated gas separation membraneis heated at about 10° C. to about 150° C.; preferably at about 10° C.to about 100°; more preferably at about 30° and about 70° C. In analternative embodiment, the coating material is heated prior to coatingit on the unmodified gas separation membrane. In another embodiment, themembrane is also heated prior to coating with the heated coatingmaterial.

The heated coated gas separation membrane is further contacted with atleast one oxidizing agent for a time effective to surface modify the gasseparation membrane between about 5 minutes and 24 hours to produce thesurface modified gas separation membrane having improvedpermselectivity; preferably between about 10 minutes to about 5 hours,more preferably between about 15 minutes to about 2 hours. The timerequired to modify the membrane will depend upon the concentration ofthe oxidizing agent used; lower concentrations will require longerexposure times. In an alternative embodiment, the surface modified gaspermeable membrane is further subjected to additional ozonizationtreatment for a time effective to further modify the gas separationmembrane.

The oxidizing agent is ozone. In one embodiment, the oxidizing agent ispresent as a gas mixture. The gas mixture may be optionally diluted withoxygen or an inert gas such as nitrogen or helium. In an alternativeembodiment, the oxidizing agent is present as an aqueous solution. Inone embodiment, the oxidizing agent is present in a concentration of1000 ppm to about 20,000 ppm, preferably at a concentration of about1000 ppm to about 15,000 ppm, and most preferably at a concentration ofabout 1000 ppm to about 10,000 ppm. In another embodiment, the flow rateof the ozone containing gas is in the range of about 2 to about 200liters/minute, preferably about 4 to about 100 liters/minute, and morepreferably about 6 to about 100 liters/minute; at pressure in the rangeof about 2 to about 100 psi. The amount of ozone that reacts with apolymeric gas separation membrane or a coating material is referred toas “ozone-uptake,” and can be measured by methods well known in the art,such measurement of weight changes, measurement of spectroscopic (e.g.,UV, IR, NMR, ESCA, and the like) signatures for production of oxidizedspecies, total elemental analysis, and the like. A preferred method isto measure the increase in weight of the membrane after the membrane hasbeen treated with ozone.

The permselectivity of the surface modified gas separation membrane isincreased by about 5% as compared to the surface unmodified membrane,preferably, the permselectivity is increased by about 20% as compared tothe surface unmodified membrane, and more preferably, thepermselectivity is increased by about 30% as compared to the surfaceunmodified membrane. The surface treatment results in an increase in gasselectivity with a commercially acceptable decrease in gas permeability.

The modified gas permeable membrane can be used to separate gas mixturesinto enriched and depleted streams. The surface modified membranes areincorporated into plate, frame, spiral, or hollow fiber devices. Methodsof fabricating such devices are known in the art. The fabricatedmembrane device is placed in an appropriate pressure vessel, and themodified surface of the gas separation membrane is contacted with thefeed gas mixture. Such membrane separations are based on relativepermeabilities of various components of the fluid mixture, resultingfrom a gradient of driving forces, such as pressure, partial pressure,concentration and temperature. Such selective permeation results in theseparation of the fluid mixture into retentate, i.e. slowly permeablecomponents, and permeate portions, i.e. faster migrating components. Thepermeate gas is then removed from the downstream side of the gasseparation membrane. Preferably, the separation takes place attemperatures between about 0° C. and about 150° C. In a preferredembodiment, the surface-modified membranes of the invention are usefulin separating a gas mixture of one or more gases. The gas mixturepreferably comprises at least one of the gases selected from the groupconsisting of hydrogen, helium, oxygen, nitrogen, carbon monoxide,carbon dioxide, hydrogen sulfide, ammonia, methane, other lighthydrocarbons, and the like. Light hydrocarbons as used herein refers toC₁₋₁₄ containing saturated and unsaturated hydrocarbons. Examples ofsuch gases being separated are hydrogen and/or helium from lighthydrocarbons, oxygen from nitrogen, nitrogen from methane, carbonmonoxide and/or carbon dioxide from light hydrocarbons, and the like.

The surface modified gas separation membrane has a carbon dioxide fluxpreferably of about 20, more preferably of about 25. The surfacemodified gas separation membrane has a separation factor for carbondioxide/ methane preferably of about 35, more preferably of about 40.The surface modified gas separation membrane has an oxygen fluxpreferably of about 2, more preferably of about 4. The surface modifiedgas separation membrane has a separation factor for oxygen/nitrogenpreferably of about 7, more preferably of about 8.

In general, to prepare asymmetric gas separation membranes, the desiredpolymeric material is dissolved in a suitable solvent system at adesired concentration. The membrane is then spun from the solution, thesolvent is partially evaporated and the fiber is coagulated, solidifiedand leached in a nonsolvent, preferably water, to obtain the gasseparation membrane. The gas separation membrane is collected on aspool, woven, cut into desired lengths, treated to remove solvents anddried. A gas separation device is prepared from the fiber. The gasseparation membranes in the device are then coated with a solution ofthe coating material, wherein the coating solution may be optionallyheated prior to coating the membrane. The coated membrane device is thenoptionally treated to remove excess coating material and furtheroptionally treated to remove solvents. The coated gas separationmembrane device is heated at about 10° C. to about 150° C. for anappropriate period of time ranging from 5 minutes to 24 hours. Theheated, coated gas separation membrane device is then subjected toozonization as follows.

The heated, coated gas separation membrane device is exposed to anozone-oxygen mixture, or ozone in admixture with other carrier gases aswell, such as, for example, oxygen/nitrogen mixtures, nitrogen, helium,argon and the like. The oxidative reaction may be carried out bysubjecting the gas separation membrane to ozone. Alternatively, theoxidant may be first dissolved in an appropriate liquid material. Thegas separation membrane is then brought into contact with the oxidantcontaining liquid. The effective concentration of the oxidizing agentwill depend on the reactivity of the polymer, the exposure time and thedesired selectivity and permeability properties of the membrane. Ingaseous carriers the concentration of ozone ranges from about 0.01 wt. %to about 10 wt. %, preferably from about 0.01 wt. % to about 5 wt. %,and more preferably from about 0.05 to about 1.0 wt. %. In a liquidcarrier, the concentration is determined by the partition coefficient ofozone from the gas phase into the carrier consistent with the gas phaseconcentrations listed above. The heated, coated gas separation membraneis exposed to the ozone for a period of time ranging from about fiveminutes to about twenty-four hours, again depending on the reactivity ofthe polymer, the concentration of ozone, the temperature and the desiredselectivity. In a preferred embodiment, ozone in a carrier gas isbrought into contact with the heated coated membrane. Thesurface-modified membrane may be optionally treated with a non-oxidizinggas for an effective period of time to remove substantially all of theoxidizing gas to produce the surface modified gas separation membranehaving improved permselectivity. In an alternative embodiment, thesurface modified gas permeable membrane is further exposed to additionalozonation treatment for a desired amount of time to further modify thegas separation membrane.

The following examples are illustrative in nature, and are not intendedto limit the scope of the present invention in any manner.

EXAMPLE 1

Hollow membrane fibers were manufactured by wet/dry spinning of asolution of tetrabromo-bis(4-hydroxyphenyl)fluorene polycarbonate(TBBHPF PC) (40% weight of total solution) dissolved in a mixture(2.2/1.0 weight/weight ratio) of N-methylpyrrolidone (NMP) andtriethylene glycol (TEG), which mixture comprised 60% weight of thetotal polymer solution.

The polymer solution was extruded through a multi-hole spinnerette attemperatures between about 50° C. to about 80° C., while injecting airinto the pin of the spinnerette to form the bore of the hollow fiber.The fiber was passed through an air gap of about 15 cm (6 inches) anddipped into a liquid quench bath at a temperature of about 0-10° C. for1-2 minutes. After coagulation, the solid asymmetric hollow fibermembrane was leached in water at 80°-100°C. for 2-5 minutes andsubsequently collected on a spool. The fiber was removed from the spool,woven into a mat, cut to the desired length and annealed at about80°130° C. for about 5-55 minutes. These fibers were inserted into atest device, and tested for membrane permeation properties, using testgases nitrogen and oxygen at about 50 psi gas pressure differentialacross the fiber wall at test temperature in the range of 25°-40° C.

The test device comprised a pressure vessel with four ports: first andsecond tubesheet ports, and third and fourth unobstructed ports. In aboreside feed module, the compressed gas is introduced into the vesselthrough the first tubesheet port, and removed/purged from the vesselthrough the second tubesheet port; the permeate is removed from thethird and fourth unobstructed ports. In a shellside feed module, thecompressed gas is introduced into the vessel through the thirdunobstructed port, and is removed/purged from the vessel through thefourth unobstructed port; the permeate is removed from the first andsecond tubesheet ports.

The test devices were operated at 25° C., consistent with a shellsidefeed configuration, purged and then pressurized with nitrogen at 50psig. When the exit port (fourth unobstructed port) is closed and thefeed port (third unobstructed port) opened, due to a pressure drivingforce, the gas contained within the test device permeates through thewalls of the hollow fibers and passes through the lumen of the fibersand exits through the first and second tubesheet ports, where the flowrate was measured by means of bubble-flow meter. Negligible backpressure was observed on the gas exiting the tubesheets. Following thenitrogen testing, the feed gas was changed to oxygen and the vessel waspurged for about two minutes to give pure oxygen at 50 psig in the testdevice. The amount of oxygen permeating through the fiber walls wasmeasured by combining the outputs from the first and second tubesheetports.

(A) Surfactant-coated Fibers

The test devices were then placed in holders and, consistent withboreside feed configuration, tubing was attached to the feed port (firsttubesheet port), non-permeate port (second tubesheet port) and permeateports (third and fourth unobstructed ports). The test devices wereconnected in parallel. Nitrogen (50 psig) was used to force a solutionof Triton X-100 in water (400 ml at 150 ppm) down the bore of the hollowfibers in the test devices (the back-pressure was adjusted to 10 lbs).The test devices were purged with nitrogen for 15 to 20 minutes. Thetest devices were then heated at 50° C. for 30 minutes, removed fromtheir holders and set aside for 1 hour before testing the units fornitrogen and oxygen flow.

(B) Ozonization of Fibers

TBBHPF PC fibers with and without surfactant-coating were treated asfollows. The test devices were then placed in holders and, consistentwith boreside feed configuration, tubing was attached to the feed port(first tubesheet port), non-permeate port (second tubesheet port) andpermeate ports (third and fourth unobstructed ports). The test deviceswere immersed in a water bath maintained at 40° C. The test devices wereconnected in series with the non-permeate flow from test device #1becoming the feed flow for the second test device while permeate portsare closed. Oxygen was passed through an ozone generation unit, andozone was passed down the bore of the hollow fibers in the test devicesat the desired ozone concentration (ppm) level. The pressure was set at9 psig and the flow rate was set to 15 standard cubic feet/hour (scfh).The hollow fibers in the test devices were exposed to the specifiedlevel of ozone for a fixed period of time. The test devices weresubsequently purged with oxygen for 15 to 20 minutes. The test deviceswere then removed from the water bath, removed from their holders andset aside for 1 hour before retesting the units for nitrogen and oxygenflow.

TBBHPF PC fibers, with and without surfactant coating were testedaccording to the above-described methods. The results, before and aftertreatment with ozone, are listed in Table 1.

TABLE 1 Initial O₂ Initial O₃ Conc. Time Final O₂ Final Test (GPU) Alpha(ppm) (min) (GPU) Alpha 1^(a) 46.1 4.47  4725 120 1.10 9.12 2^(a) 44.44.50  4725 120 1.19 8.10 3^(b) 140.4 2.0 13690  50 11.4 3.52 4^(b) 151.11.9 13690  50 10.5 3.40 ^(a)Surfactant-coated TBBHPF PC fibers^(b)TBBHPF PC fibers

As illustrated in Table 1, surface modified membranes have an improvedpermselectivity as compared to the surface unmodified membranes.Further, coating the surface unmodified membrane prior to surfacemodification also results in an increase in the permselectivity value,i.e. the alpha value, as compared to the permselectivity value of thesurface unmodified, uncoated membrane.

EXAMPLE 2

Surfactant-coated TBBHPF PC fibers were tested according to theabove-described methods. The modified surfactant-coated TBBHPF PC fiberswere subjected to additional ozonization treatment anf retested forpermeability. The results are listed in Table 2.

TABLE 2 Initial O₂ Initial O₃ Conc. Time Final O₂ Final Test (GPU) Alpha(ppm) (min) (GPU) Alpha 5^(a) 42.7 4.6 2212 120 3.4 8.0 6^(b) 3.4 8.03000 120 0.9 10.3 ^(a)Single ozone treatment ^(b)Multiple ozonetreatment

As illustrated in Table 2, multiple ozonization treatment furtherimproves the permselectivity value of the surface modified membrane ascompared to the permselectivity value of the surface unmodifiedmembrane.

EXAMPLE 3

Tetrabromo-bisphenol A polycarbonate (TBBA PC) fibers, with and withoutsurfactant coating, were tested according to the above-describedmethods. The results, before and after treatment with ozone, are listedin Table 3.

TABLE 3 Initial O₂ Initial O₃ Conc. Time Final O₂ Final Test (GPU) Alpha(ppm) (min) (GPU) Alpha 8^(a) 19.5 6.92 4875 105 15.8 6.78 8^(a) 20.26.39 4875 105 15.8 6.46 10^(b)  13.9 7.7 7875 120 8.5 8.2 ^(a)TBBA PCfibers ^(b)Surfactant-coated TBBA PC fibers

As illustrated in Table 3, the permselectivity value of the surfacemodified membrane is greater than the intrinsic value of the surfaceunmodified membrane.

Thus, a method for preparing a surface modified gas separation membrane,wherein said membrane has improved permselective properties to separatea mixture of gases as compared to the unmodified membrane is disclosed.Although preferred embodiments of the invention have been described insome detail, it is understood that obvious variations can be madewithout departing from the spirit and scope of the invention as definedby the appended claims.

We claim:
 1. A surface-modified gas separation membrane having improvedpermselectivity properties for separating a mixture of gases as comparedto an unmodified member, and further wherein said membrane is a hollowfiber membrane adapted for boreside feed, the surface-modified gasseparation membrane produced by a process comprising the steps of: (a)providing a surface unmodified gas separation membrane; (b) providing asolution of a coating material, wherein said coating material is anorganic material having at least one site of unsaturation; (c)contacting the surface unmodified gas separation membrane with thesolution of the coating material; (d) coating said coating material onthe surface unmodified gas separation membrane by passing a solution ofthe coating material through the bore of the hollow fiber membrane toproduce a coated gas separation membrane; (e) optionally removingsubstantially all of the residual coating material from the surface ofthe coated gas separation membrane of step (d); (f) optionally removingsubstantially all of the solvent from the surface of the coated gasseparation membrane of step (d) or (e) by contacting the surface with atleast one anhydrous non-oxidizing gas; (g) heating the coated gasseparation membrane of step (d), (e), or (f) at about 10° C. to about150° C.; (h) contacting the heated coated gas separation membrane ofstep (g) with at least one oxidizing agent for a time effective tosurface modify the gas separation membrane between about 5 minutes and24 hours to produce the surface modified gas separation membrane havingimproved permselectivity, wherein the oxidizing agent is oxygen, ozoneor combinations thereof; and (i) optionally contacting the surfaceoxidized gas separation membrane of step (h) with a non-oxidizing gasfor a time effective to remove substantially all of the oxidizing gas toproduce the surface modified gas separation membrane having improvedpermselectivity.
 2. The method of claim 1, wherein the process furthercomprises: (j) contacting the treated gas separation membrane of step(h) or (i) further with at least one oxidizing agent for a timeeffective to surface modify the gas separation membrane between about 5minutes and 24 hours to produce the surface modified gas separationmembrane having improved permselectivity, wherein the oxidizing agent isoxygen, ozone or combinations thereof; and (k) optionally contacting thesurface oxidized gas separation membrane of step (j) with anon-oxidizing gas for a time effective to remove substantially all ofthe oxidizing agent to produce the surface modified gas separationmembrane having improved permselectivity.
 3. The gas separation membraneof claim 1, wherein the hollow fibre membrane is an asymmetric hollowfiber.
 4. The gas separation membrane of claim 1, wherein the organicmaterial is a low molecular weight polymeric material, wherein themolecular weight ranges from about 1000 to about 100,000.
 5. The gasseparation membrane of claim 1, wherein the organic material is asurfactant.
 6. The gas separation membrane of claim 1, wherein thepermselectivity of the surface modified gas separation membrane isincreased by about 5% to about 30% as compared to the permselectivity ofthe surface unmodified membrane.
 7. The gas separation membrane of claim1, wherein the oxidizing agent is present as a gas.
 8. The gasseparation membrane of claim 1, wherein the oxidizing agent is presentas an aqueous solution.
 9. The gas separation membrane of claim 1,wherein the oxidizing agent is present in a concentration of 1000 ppm toabout 20,000 ppm.
 10. The gas separation membrane of claim 1, whereinflow rate of the oxidizing agent is about 2 to about 200 liters/minute.11. The gas separation membrane of claim 1, wherein the non-oxidizinggas is selected from nitrogen, air, helium, carbon dioxide andcombinations thereof.
 12. The gas separation membrane of claim 11,wherein the non-oxidizing gas is nitrogen.
 13. The gas separationmembrane of claim 1, the coated gas separation membrane is heated atabout 30° C. to about 70° C.
 14. The gas separation membrane of claim13, wherein the coated gas separation membrane is heated at about 30° C.and about 70° C.
 15. The gas separation membrane of claim 1, wherein thetime effective to surface modify the gas separation membrane is betweenabout 10 minutes to about 5 hours.
 16. The gas separation membrane ofclaim 1, wherein the time effective to surface modify the gas separationmembrane is between about 15 minutes to about 2 hours.
 17. The gasseparation membrane of claim 1, wherein said membrane is a hollow fibermembrane adapted for boreside feed, the gas separation membranecomprising: (a) providing a surface unmodified gas separation membrane;(b) providing a solution of a coating material, wherein said coatingmaterial is an organic material having at least one site ofunsaturation; (c) heating the solution of the coating material at about10° C. to about 150° C.; (d) optionally heating the surface unmodifiedgas separation membrane at about 10° C. to about 150° C.; (e) contactingthe surface unmodified gas separation membrane with the heated solutionof the coating material; (f) coating said heated coating material on thesurface unmodified gas separation membrane by passing a solution of thecoating material through the bore of the hollow fiber membrane toproduce a coated gas separation membrane; (g) optionally removingsubstantially all of the residual coating material from the surface ofthe coated gas separation membrane of step (f); (h) optionally removingsubstantially all of the solvent from the surface of the coated gasseparation membrane of step (f) or (g) by contacting the surface with atleast one anhydrous non-oxidizing gas; (i) contacting the heated coatedgas separation membrane of step (f), (g), or (h) with at least oneoxidizing agent for a time effective to surface modify the gasseparation membrane between about 5 minutes and 24 hours to produce thesurface modified gas separation membrane having improvedpermselectivity, wherein the oxidizing agent is oxygen, ozone orcombinations thereof; and (j) optionally contacting the surface oxidizedgas separation membrane of step (i) with a non-oxidizing gas for a timeeffective to remove substantially all of the oxidizing gas to producethe surface modified gas separation membrane having improvedpermselectivity.
 18. The gas separation membrane of claim 17, producedby a method further comprising: (k) contacting the treated gasseparation membrane of step (i) or (j) further with at least oneoxidizing agent for a time effective to surface modify the gasseparation membrane between about 5 minutes and 24 hours to produce thesurface modified gas separation membrane having improvedpermselectivity, wherein the oxidizing agent is oxygen, ozone orcombinations thereof; and (l) optionally contacting the surface oxidizedgas separation membrane of step (k) with a non-oxidizing gas for a timeeffective to remove substantially all of the oxidizing agent to producethe surface modified gas separation membrane having improvedpermselectivity.